CN103534290B - 含胺二氟代苯并三唑基聚合物及其制备方法和应用 - Google Patents
含胺二氟代苯并三唑基聚合物及其制备方法和应用 Download PDFInfo
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- CN103534290B CN103534290B CN201180070754.9A CN201180070754A CN103534290B CN 103534290 B CN103534290 B CN 103534290B CN 201180070754 A CN201180070754 A CN 201180070754A CN 103534290 B CN103534290 B CN 103534290B
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- Prior art keywords
- difluoride
- triazolyl
- polymkeric substance
- amine phenyl
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- 150000001412 amines Chemical class 0.000 title claims abstract description 39
- 239000000126 substance Substances 0.000 title claims abstract description 39
- 125000001425 triazolyl group Chemical group 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 36
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 30
- 229910052763 palladium Inorganic materials 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 15
- 238000005859 coupling reaction Methods 0.000 claims description 12
- OMFXVFTZEKFJBZ-HJTSIMOOSA-N corticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OMFXVFTZEKFJBZ-HJTSIMOOSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000003446 ligand Substances 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 36
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 abstract description 12
- 125000000217 alkyl group Chemical group 0.000 abstract description 8
- 238000012546 transfer Methods 0.000 abstract description 7
- 239000012964 benzotriazole Substances 0.000 abstract description 5
- 125000000524 functional group Chemical group 0.000 abstract description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 abstract description 3
- 239000011737 fluorine Substances 0.000 abstract description 3
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 0 *Oc(cc1)ccc1N(c1ccc(C=C)cc1)c1ccc(C=C)cc1 Chemical compound *Oc(cc1)ccc1N(c1ccc(C=C)cc1)c1ccc(C=C)cc1 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 6
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- 238000003756 stirring Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- -1 n-hexadecyl Chemical group 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- FPLGMKDFWCAWSZ-UHFFFAOYSA-N CCCCCCCC[n](c(C)c1c(-c([s]2)ccc2Br)c2F)nc1c(-c([s]1)ccc1Br)c2F Chemical compound CCCCCCCC[n](c(C)c1c(-c([s]2)ccc2Br)c2F)nc1c(-c([s]1)ccc1Br)c2F FPLGMKDFWCAWSZ-UHFFFAOYSA-N 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
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- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
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Abstract
本发明属于太阳能电池领域，其公开了一种含胺二氟代苯并三唑基聚合物及其制备方法和应用；该太阳能电池材料具有下述结构式（I）：式（I）中，R1、R2均为C1～C20的烷基，n为10～50的整数。本发明提供的含胺二氟代苯并三唑基聚合物，由于1,2,3-苯并三唑太阳能电池材料含有两个氟原子，其HOMO能级将降低0.11eV，而氟取代的1,2,3-苯并三唑又有两个强吸电子的亚胺基，1,2,3-苯并三唑是一个有强吸电子性能的杂环化合物，且苯并三唑的N-H键的N上容易引入烷基链，该烷基链官能性基团可以提高太阳能的能量转换效率，从而解决太阳能电池材料太阳能电池低效率问题。
Description
技术领域
本发明涉及太阳能电池材料领域，尤其涉及一种含胺二氟代苯并三唑基聚合物及其制备方法和应用。
背景技术
利用廉价材料制备低成本、高效能的太阳能电池一直是光伏领域的研究热点和难点。目前用于地面的硅晶电池由于生产工艺复杂、成本高，使其应用受到限制。为了降低电池成本，拓展应用范围，长期以来人们一直在寻找新型的太阳能电池材料。有机半导体材料以其原料易得、廉价、制备工艺简单、环境稳定性好、有良好的光伏效应等优点备受关注。自1992年N.S.Sariciftci等在SCIENCE（N.S Sariciftci,L.Smilowitz,A.J.Heeger,etal.Science,1992,258,1474）上报道共轭有机半导体材料与C60之间的光诱导电子转移现象后，人们在聚合物太阳能电池方面投入了大量研究，并取得了飞速的发展，但是仍比无机太阳能电池的转换效率低得多。
发明内容
本发明的目的一在于提供一种能量转换效率高的含胺二氟代苯并三唑基聚合物。
一种具有下述结构式（I）的含胺二氟代苯并三唑基聚合物：
式中，R1、R2均为C1～C20的烷基，n为10～50的整数，优选n为30～40。
本发明的另一目的在于提供上述含胺二氟代苯并三唑基聚合物的制备方法，包括如下步骤：
S1、分别提供如下结构式表示的化合物A和化合物B，
其中，所述化合物A中，R1为C1～C20的烷基；所述化合物B中，R2为C1～C20的烷基；
S2、在无氧环境下，将所述化合物A和化合物B按照摩尔比1:1加入量，添加入含有催化剂的有机溶剂中，于70～130℃下进行Heck耦合反应24～96小时后，得到具有下述结构式（I）的所述含胺二氟代苯并三唑基聚合物：
式中，n为10～50的整数。
上述含胺二氟代苯并三唑基聚合物的制备方法还包括如下步骤：
S3、对步骤S2中制得的含胺二氟代苯并三唑基聚合物进行纯化处理。
在上述含胺二氟代苯并三唑基聚合物的制备方法的步骤S2中：
所述催化剂为有机钯，或者为有机钯与有机磷配体的混合物；所述有机钯与所述化合物A的摩尔比为1:20～1:100；其中，所述有机钯选自双三苯基膦二氯化钯、四三苯基膦钯及醋酸钯中的至少一种；所述有机磷配体为三邻甲苯基膦；
所述有机溶剂选自甲苯、N,N-二甲基甲酰胺及四氢呋喃中的至少一种。
优选地，所述步骤S2中：
所述Heck耦合反应温度为90～120℃；所述Heck耦合反应时间为48～72h。
本发明的又一目的在于提供上述含胺二氟代苯并三唑基聚合物在有机太阳能电池中的应用。
本发明提供的含胺二氟代苯并三唑基聚合物，由于1,2,3-苯并三唑太阳能电池材料含有两个氟原子，其HOMO能级将降低0.11eV，而氟取代的1,2,3-苯并三唑又有两个强吸电子的亚胺基，1,2,3-苯并三唑是一个有强吸电子性能的杂环化合物，且苯并三唑的N-H键的N上容易引入烷基链，该烷基链官能性基团可以提高太阳能的能量转换效率，从而解决太阳能电池材料太阳能电池低效率问题，同时，烷基链官能性基团还可以起到调节含胺二氟代苯并三唑基聚合物的溶解性，使得该太阳能电池材料有利于成膜加工，扩大它们在太阳能电池材料太阳能电池领域的应用范围。
附图说明
图1为本发明含胺二氟代苯并三唑基聚合物的制备工艺流程图；
图2为实施例2制备的聚{4,4’-二乙烯对甲氧基苯基二苯胺-co-2-正二十烷基-4,7-二噻吩基-5,6-二氟苯并三唑}的紫外可见吸收光谱图；
图3为实施例4的有机太阳能电池结构示意图。
具体实施方式
本发明提供的具有下述结构式（I）的含胺二氟代苯并三唑基聚合物：
式中，R1、R2均为C1～C20的烷基，n为10～50的整数；n优选为30～40。
上述含胺二氟代苯并三唑基聚合物的制备方法，如图1所示，包括如下步骤：
S1、分别提供如下结构式表示的化合物A和化合物B，
即4,4’-二乙烯对烷氧基苯基二苯胺；
即2-烷基-4,7-二(5-溴噻吩基)-5,6-二氟-1,2,3-苯并三唑；
其中，化合物A中，R1为C1～C20的烷基；化合物B中，R2为C1～C20的烷基；
S2、在无氧环境（如，氮气、氩气或氮气和氩气混合气等构成的无氧环境）下，将所述化合物A和化合物B按照摩尔比1:1加入量，添加入含有催化剂的有机溶剂中，于70～130℃下进行Heck耦合反应24～96小时后，得到反应液，该反应液中包含产物，即具有下述结构式（I）的所述含胺二氟代苯并三唑基聚合物：
式中，n为10～50的整数；
S3、对步骤S2中的产物进行纯化处理：
往步骤S2的反应液中加入甲醇，进行沉析处理，随后用索氏提取器过滤，之后依次用甲醇和正己烷抽提沉淀24h；然后继续以氯仿为溶剂抽提沉淀至无色，收集氯仿溶液并旋干得到红色粉末，将红色粉末在真空下50℃干燥24h后，得到纯化的含胺二氟代苯并三唑基聚合物。
在上述含胺二氟代苯并三唑基聚合物的制备方法，所述步骤S2中：
所述催化剂为有机钯，或者为有机钯与有机磷配体的混合物；所述有机钯与所述化合物A的摩尔比为1:20～1:100；其中，所述有机钯选自双三苯基膦二氯化钯、四三苯基膦钯及醋酸钯中的至少一种；所述有机磷配体为三邻甲苯基膦；有机钯与有机磷配体的混合物中，有机钯与有机磷配体的摩尔比为1:3～1:6。
所述有机溶剂选自甲苯、N,N-二甲基甲酰胺及四氢呋喃中的至少一种。
优选地，所述步骤S2中：
所述Heck耦合反应温度为90～120℃；所述Heck耦合反应时间为48～72h。
本发明提供的含胺二氟代苯并三唑基聚合物，由于1,2,3-苯并三唑太阳能电池材料含有两个氟原子，其HOMO能级将降低0.11eV，而氟取代的1,2,3-苯并三唑又有两个强吸电子的亚胺基，1,2,3-苯并三唑是一个有强吸电子性能的杂环化合物，且苯并三唑的N-H键的N上容易引入烷基链，该烷基链官能性基团可以提高太阳能的能量转换效率，从而解决太阳能电池材料太阳能电池低效率问题，同时，烷基链官能性基团还可以起到调节含胺二氟代苯并三唑基聚合物的溶解性，使得该太阳能电池材料有利于成膜加工，扩大它们在太阳能电池材料太阳能领域的应用范围。
另外，本发明的制备方法，采用较简单的合成路线，从而减少工艺流程，材料价廉易得，降低制造成本。
上述含胺二氟代苯并三唑基聚合物可以应用在有机太阳能电池的活性层中。
为了更好地理解本发明专利的内容，下面通过具体的实例和图例来进一步说明本发明的技术案，具体包括材料制备和器件制备，但这些实施实例并不限制本发明，其中化合物A的单体从市场上购买得到，化合物B的单体可参照文献（J.Am.Chem.Soc.2011,133,4625）制备或者从市场上购买得到。
实施例1
本实施例的含胺二氟代苯并三唑基聚合物，即聚{4,4’-二乙烯对正辛氧基苯基二苯胺-co-2-正辛基-4,7-二噻吩基-5,6-二氟苯并三唑}，其中，R1为正辛烷基，R2为正辛烷基，n为37；其结构式如下：
上述太阳能电池材料的制备步骤如下：
反应式如下所示：
将，4,4’-二乙烯对正辛氧基苯基二苯胺(89mg,0.3mmol)、2-正辛基-4,7-二(5-溴噻吩基)-5,6-二氟-1,2,3-苯并三唑(1768mg,0.3mmol)、醋酸钯(10.1mg,0.015mmol)以及三邻甲氧基膦(3mg)加入盛有12mL N,N-二甲基甲酰胺的烧瓶中，溶解成溶液，向烧瓶中充分通氮气排空气约30min后，在120℃下搅拌、Heck耦合反应48h，降温后停止聚合反应，获得反应液。
向烧瓶中加入40mL甲醇，对反应液进行沉析处理，接着通过索氏提取器过滤，之后依次用甲醇和正己烷抽提沉淀24h；然后继续以氯仿为溶剂抽提沉淀至无色，收集氯仿溶液并旋干得到红色粉末，最后将收集后的红色粉末在真空下50℃干燥24h后即为聚{4,4’-二乙烯对正辛氧基苯基二苯胺-co-2-正辛基-4,7-二噻吩基-5,6-二氟苯并三唑}产物，产率为58%。
测试结果为：Molecular weight(GPC,THF,R.I):Mn=31.6kDa,Mw/Mn=2.2。
实施例2
本实施例的含胺二氟代苯并三唑基聚合物，即聚{4,4’-二乙烯对甲氧基苯基二苯胺-co-2-正二十烷基-4,7-二噻吩基-5,6-二氟苯并三唑}，其中，R1为甲基，R2为正二十烷基，n为30，其结构式如下：
上述太阳能电池材料的制备步骤如下：
反应式如下所示：
将4,4’-二乙烯对甲氧基苯基二苯胺(65mg,0.2mmol)和2-正二十烷基-4,7-二(5-溴噻吩基)-5,6-二氟-1,2,3-苯并三氮唑(151.4mg,0.2mmol)加入盛有15ml甲苯的烧瓶中，溶解成溶液，抽真空烧瓶除氧并充入氩气，然后加入5mg双三苯基膦二氯化钯，在100℃下搅拌、Heck耦合反应60h，降温后停止聚合反应，获得反应液。
向烧瓶中加入50mL甲醇，对反应液进行沉析处理，接着通过索氏提取器过滤，之后依次用甲醇和正己烷抽提沉淀24h；然后继续以氯仿为溶剂抽提沉淀至无色，收集氯仿溶液并旋干得到红色粉末，最后将收集后的红色粉末在真空下50℃干燥24h后即为聚{4,4’-二乙烯对甲氧基苯基二苯胺-co-2-正二十烷基-4,7-二噻吩基-5,6-二氟苯并三唑}产物，产率52%。
测试结果为：Molecular weight(GPC,THF,R.I):Mn=28.6kDa,Mw/Mn=2.2。
图2为实施例2制备的聚{4,4’-二乙烯对甲氧基苯基二苯胺-co-2-正二十烷基-4,7-二噻吩基-5,6-二氟苯并三唑}的紫外可见吸收光谱图；由图2可以看出共轭聚合物在640nm左右处有较强的吸收峰。
实施例3
本实施例的含胺二氟代苯并三唑基聚合物，即聚{4,4’-二乙烯对正二十烷氧基苯基二苯胺-co-2-甲基-4,7-二噻吩基-5,6-二氟苯并三唑}，其中，R1为二十烷基，R2为甲烷基，n为40，其结构式如下：
上述太阳能电池材料的制备步骤如下：
反应式如下所示：
将4,4’-二乙烯对正二十烷氧基苯基二苯胺(178mg,0.3mmol)和2-甲基-4,7-二(5-溴噻吩基)-5,6-二氟-1,2,3-苯并三氮唑(147.3mg,0.3mmol)加入盛有15mL四氢呋喃的50mL规格的两口瓶中，溶解成溶液，向两口瓶中充分通氮气和氩气混合气，排空气约20min后，然后将17mg四三苯基膦钯加入两口瓶中，再充分通氮气和氩气混合气排空气约10min后,在90℃下搅拌、Heck耦合反应72h，获得反应液。
向烧瓶中加入40mL甲醇，对反应液进行沉析处理，接着通过索氏提取器过滤，之后依次用甲醇和正己烷抽提沉淀24h；然后继续以氯仿为溶剂抽提沉淀至无色，收集氯仿溶液并旋干得到红色粉末，最后将收集后的红色粉末在真空下50℃干燥24h后即为聚{4,4’-二乙烯对正二十烷氧基苯基二苯胺-co-2-甲基-4,7-二噻吩基-5,6-二氟苯并三唑}产物，产率为50%。
测试结果为：Molecular weight(GPC,THF,R.I):Mn=37.0kDa,Mw/Mn=2.2。
实施例4
本实施例的含胺二氟代苯并三唑基聚合物，即聚{4,4’-二乙烯对正己氧基苯基二苯胺-co-2-正十六烷基-4,7-二噻吩基-5,6-二氟苯并三唑}，其中，R1为正己基，R2为正十六烷基，n为10，其结构式如下：
上述太阳能电池材料的制备步骤如下：
反应式如下所示：
将4,4’-二乙烯对正己氧基苯基二苯胺(79.4mg,0.2mmol)和2-正十六烷基-4,7-二(5-溴噻吩基)-5,6-二氟-1,2,3-苯并三氮唑(140mg,0.2mmol)加入盛有15ml甲苯的烧瓶中，溶解成溶液，抽真空烧瓶除氧并充入氩气，然后加入双三苯基膦二氯化钯（0.01mmol,7.02mg），在130℃下搅拌、Heck耦合反应24h，降温后停止聚合反应，获得反应液。
向烧瓶中加入50mL甲醇，对反应液进行沉析处理，接着通过索氏提取器过滤，之后依次用甲醇和正己烷抽提沉淀24h；然后继续以氯仿为溶剂抽提沉淀至无色，收集氯仿溶液并旋干得到红色粉末，最后将收集后的红色粉末在真空下50℃干燥24h后即为聚{4,4’-二乙烯对正己氧基苯基二苯胺-co-2-正十六烷基-4,7-二噻吩基-5,6-二氟苯并三唑}产物，产率45%。
测试结果为：Molecular weight(GPC,THF,R.I):Mn=11.4kDa,Mw/Mn=2.3。
实施例5
本实施例的含胺二氟代苯并三唑基聚合物，即聚{4,4’-二乙烯对正丁氧基苯基二苯胺-co-2-正十四烷基-4,7-二噻吩基-5,6-二氟苯并三唑}，其中，R1为正丁基，R2为正十四烷基，n为50，其结构式如下：
上述太阳能电池材料的制备步骤如下：
反应式如下所示：
将4,4’-二乙烯对正丁氧基苯基二苯胺(111mg,0.3mmol)和2-正十四烷基-4,7-二(5-溴噻吩基)-5,6-二氟-1,2,3-苯并三氮唑(202mg,0.3mmol)加入盛有15mL四氢呋喃的50mL规格的两口瓶中，溶解成溶液，向两口瓶中充分通氮气和氩气混合气，排空气约20min后，然后将四三苯基膦钯(0.003mmol,3.7mg)加入两口瓶中，再充分通氮气和氩气混合气排空气约10min后,在70℃下搅拌、Heck耦合反应96h，获得反应液。
向烧瓶中加入40mL甲醇，对反应液进行沉析处理，接着通过索氏提取器过滤，之后依次用甲醇和正己烷抽提沉淀24h；然后继续以氯仿为溶剂抽提沉淀至无色，收集氯仿溶液并旋干得到红色粉末，最后将收集后的红色粉末在真空下50℃干燥24h后即为聚{4,4’-二乙烯对正丁氧基苯基二苯胺-co-2-正十四烷基-4,7-二噻吩基-5,6-二氟苯并三唑}产物，产率为72%。
测试结果为：Molecular weight(GPC,THF,R.I):Mn=44.0kDa,Mw/Mn=2.0。
实施例6
本实施例6的有机太阳能电池，其采用实施例2制得的聚{4,4’-二乙烯对甲氧基苯基二苯胺-co-2-正二十烷基-4,7-二噻吩基-5,6-二氟苯并三唑}（即DFBTz-TPA2）为活性层的电子给体材料。
请参阅图3，该有机太阳能电池包括依次层叠的玻璃基层11、透明阳极12、中间辅助层13、活性层14以及阴极15。透明阳极12可采用氧化铟锡（简称为ITO），优选为方块电阻为10-20Ω/的氧化铟锡；中间辅助层13采用聚3,4-亚乙二氧基噻吩与聚苯乙烯-磺酸复合材料（简称为PEDOT:PSS）；活性层14包括电子给体材料和电子受体材料，电子给体材料采用实施例1制备的聚合物（即DFBTz-TPA2），电子受体材料可以是[6,6]苯基-C61-丁酸甲酯（简称为PCBM）；阴极15可采用铝电极或者双金属层电极，例如Ca/Al或Ba/Al等，其厚度优选为170nm、30nm、130nm或60nm。
玻璃基层11可作为底层，制作时，选取ITO玻璃，并经超声波清洗后，用氧-Plasma处理，在ITO玻璃上涂覆中间辅助层13，再将实施例1制备的聚合物和电子受体材料通过共混后涂覆于中间辅助层13上，形成活性层14，然后再通过真空蒸镀技术在活性层14上沉积阴极15，获得上述有机太阳能电池。该有机太阳能电池还需经过110摄氏度密闭条件下加热4小时，再降到室温，器件经过退火后能有效增加分子内各基团和分子链段间排列的有序性和规整度，提高载流子迁移率的传输速度和效率，进而提高光电转换效率。在本实施例中，阴极15Al层的厚度分别为170nm。
如图3所示，在光照下，光透过玻璃基层11和ITO电极12，活性层14中的传导空穴型电致发光材料吸收光能，并产生激子，这些激子再迁移到电子给体/受体材料的界面处，并将电子转移给电子受体材料，如PCBM，实现电荷的分离，从而形成自由的载流子，即自由的电子和空穴。这些自由的电子沿电子受体材料向金属阴极传递并被阴极所收集，自由的空穴沿电子给体材料向ITO阳极传递并被阳极所收集，从而形成光电流和光电压，实现光电转换，外接负载16时，可对其进行供电。在此过程中，传导空穴型电致发光材料由于其具有很宽的光谱响应范围，能够更充分地利用光能，以获得更高的光电转换效率，增加有机太阳能电池的产电能力。而且这种有机材料还能减轻有机太阳能电池的质量，并通过旋涂等技术即可制作，便于大批量的制备。
表1为本实施例6的有机太阳能电池的光伏属性。（注：PCE为能量转换效率，Voc为开路电压，Jsc为短路电流，FF为填充因子。）
表1
表1结果表明，在AM1.5、100mW/cm2光照下，基于DFBTz-TPA2为电子给体材料的本体异质结太阳能电池的能量转换效率为2.8%；其中，AM为大气质量是指太阳光束穿过大气层的光学路径，以该光学路径与太阳在天顶时其光束到达海平面所通过的光学路径的比值表示；AM1.5条件是指标定和测试地面用太阳能电池所规定的辐照度和光谱分布；其太阳能总辐照度为1000瓦每平方米，太阳能电池的测量温度为25度；此标准为国际电工委员会制定，我国目前采用的是此标准；具体一点来说，一个标准太阳相当于AM1.5G标准光源的辐照强度，AM1.5G表示天顶角（入射光线于入射光源与地面法线间的夹角）为48度的太阳光，光强是1000W/m2（即AM1.5、100mW/cm2光照）。
应当理解的是，上述针对本发明较佳实施例的表述较为详细，并不能因此而认为是对本发明专利保护范围的限制，本发明的专利保护范围应以所附权利要求为准。
Claims (8)
1.一种含胺二氟代苯并三唑基聚合物，具有下述结构式(I)：
式中，R1、R2均为C1～C20的烷基，n为10～50的整数。
2.根据权利要求1所述的含胺二氟代苯并三唑基聚合物，其特征在于，n为30～40。
3.一种含胺二氟代苯并三唑基聚合物的制备方法，其特征在于，包括如下步骤：
S1、分别提供如下结构式表示的化合物A和化合物B，
其中，所述化合物A中，R1为C1～C20的烷基；所述化合物B中，R2为C1～C20的烷基；
S2、在无氧环境下，将所述化合物A和化合物B按照摩尔比1:1加入量，添加入含有催化剂的有机溶剂中，于90～120℃下进行Heck耦合反应48～72h小时后，得到具有下述结构式(I)的所述含胺二氟代苯并三唑基聚合物：
式中，n为10～50的整数；
所述步骤S2中，所述有机溶剂选自甲苯、N,N-二甲基甲酰胺及四氢呋喃中的至少一种。
4.根据权利要求3所述的含胺二氟代苯并三唑基聚合物的制备方法，其特征在于，还包括如下步骤：
S3、对步骤S2制得的所述含胺二氟代苯并三唑基聚合物进行纯化处理。
5.根据权利要求3或4所述的含胺二氟代苯并三唑基聚合物的制备方法，其特征在于，所述步骤S2中，所述催化剂为有机钯，或者所述催化剂为有机钯与有机磷配体的混合物。
6.根据权利要求5所述的含胺二氟代苯并三唑基聚合物的制备方法，其特征在于，所述有机钯选自双三苯基膦二氯化钯、四三苯基膦钯及醋酸钯中的至少一种；所述有机磷配体为三邻甲苯基膦。
7.根据权利要求5所述的含胺二氟代苯并三唑基聚合物的制备方法，其特征在于，所述有机钯与所述化合物A的摩尔比为1:20～1:100。
8.权利要求1所述的含胺二氟代苯并三唑基聚合物在有机太阳能电池中的应用。
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